Water/Ethanol Displacement Reactions in Vanadyl Phosphate

Beneš, Ludvı́k; Melánová, Klára; Čapková, Pavla; Matějka, Pavel

doi:10.1002/(sici)1099-0682(199912)1999:12<2289::aid-ejic2289>3.0.co;2-u

Cited by 19 publications

(5 citation statements)

References 21 publications

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“…By comparing the Raman and FTIR spectra between the VOPO 4 ·2H 2 O precursor and Zn 0.4 VOPO 4 ·0.8H 2 O product (Figures S4 and S5), one can see that the hydrogen bond interaction between the H 2 O molecules and the PO 4 3– group was weakened in Zn 0.4 VOPO 4 ·0.8H 2 O, inducing the mitigation of the steric hindrance of O–P–O stretching vibration. Accordingly, a shift to the lower wavenumber of the symmetric O–P–O stretching modes has been observed, ,, and the relatively broader and weaker band of Zn 0.4 VOPO 4 ·0.8H 2 O compared to VOP phase suggested a lower water content . From the V 2p XPS, two split peaks among the V 2p 3/2 region of Zn 0.4 VOPO 4 ·0.8H 2 O located at 518.3 and 517.1 eV assigned to V 5+ and V 4+ have been detected, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…To better understand the chemical bonding information of this Zn 0.4 VOPO 4 •0.8H 2 O phase, Raman, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) were performed subsequently. By comparing the Raman and FTIR spectra between the Accordingly, a shift to the lower wavenumber of the symmetric O−P−O stretching modes has been observed, 21,26,27 and the relatively broader and weaker band of Zn 0.4 VOPO 4 •0.8H 2 O compared to VOP phase suggested a lower water content. 28 From the V 2p XPS, two split peaks among the V 2p 3/2 region of Zn 0.4 VOPO 4 •0.8H 2 O located at 518.3 and 517.1 eV assigned to V 5+ and V 4+ have been detected, respectively.…”

Section: Introductionmentioning

confidence: 96%

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A Layered Zn_0.4VOPO₄·0.8H₂O Cathode for Robust and Stable Zn Ion Storage

Wang

Zhang

et al. 2020

ACS Appl. Energy Mater.

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Rechargeable aqueous zinc-ion batteries (ZIBs) have shown extraordinary potential in recent years due to their prominent superiority including resource sustainability, nontoxicity, excellent energy density of the zinc anode, and better safety. Nevertheless, the development of ZIBs is still hindered by the lack of suitable cathode materials possessing a high discharge voltage, sufficient specific energy density, and long-term cycle life. Herein, our work reported a layered phosphate, Zn 0.4 VOPO 4 • 0.8H 2 O, by topochemical incorporation of zinc ions into the VOPO 4 •2H 2 O framework. The incorporation of zinc ions makes no change in the in-plane atomic arrangement and coordination environment. The resulting Zn 0.4 VOPO 4 •0.8H 2 O depicted a specific capacity of 161.4 mAh•g −1 , a discharge plateau of 1.45 V, and excellent cycling stability over 1000 cycles. The energy density of our Zn//Zn 0.4 VOPO 4 •0.8H 2 O battery was as high as 219.8 Wh•kg −1 at a power density of 136.2 W•kg −1 . A typical zinc ion intercalation/deintercalation mechanism has been revealed in this layered cathode. This work provides a layered hydrated phosphate as a robust cathode for ZIBs and also sheds light on modulation of multivalent-ion storage performance by a topochemical strategy in layered materials.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

A Layered Zn_0.4VOPO₄·0.8H₂O Cathode for Robust and Stable Zn Ion Storage

Wang

Zhang

et al. 2020

ACS Appl. Energy Mater.

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“…Raman spectra shown in Figure S2 verified the structural properties of the pure VOPO 4 ·2H 2 O bulk chunk, THF, and TEG intercalated VOPO 4 nanosheets. The bands at 937 cm –1 in the curve of pure sample were assigned to the symmetric O–P–O stretching modes. , Obviously, the symmetry of O–P–O stretching modes is strongly correlated to regional microstructures and very sensitive to the hydrogen bonding between the interlayered H 2 O molecules and V atoms. With the intercalation of THF and TEG molecules and removal of the interlayered H 2 O, the hydrogen bonds formed between the O atoms of PO bond in the layer and H 2 O were broken, inducing the mitigation of the steric hindrance and the shift of OPO stretching modes to lower energy (lower wavenumbers).…”

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confidence: 99%

Effective Interlayer Engineering of Two-Dimensional VOPO₄ Nanosheets via Controlled Organic Intercalation for Improving Alkali Ion Storage

et al. 2017

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Two-dimensional (2D) energy materials have shown the promising electrochemical characteristics for lithium ion storage. However, the decreased active surfaces and the sluggish charge/mass transport for beyond-lithium ion storage that has potential for large-scale energy storage systems, such as sodium or potassium ion storage, caused by the irreversible restacking of 2D materials during electrode processing remain a major challenge. Here we develop a general interlayer engineering strategy to address the above-mentioned challenges by using 2D ultrathin vanadyl phosphate (VOPO) nanosheets as a model material for challenging sodium ion storage. Via controlled intercalation of organic molecules, such as triethylene glycol and tetrahydrofuran, the sodium ion transport in VOPO nanosheets has been significantly improved. In addition to advanced characterization including X-ray diffraction, high-resolution transmission electron microscopy, and X-ray absorption fine structure to characterize the interlayer and the chemical bonding/configuration between the organic intercalants and the VOPO host layers, density functional theory calculations are also performed to understand the diffusion behavior of sodium ions in the pure and TEG intercalated VOPO nanosheets. Because of the expanded interlayer spacing in combination with the decreased energy barriers for sodium ion diffusion, intercalated VOPO nanosheets show much improved sodium ion transport kinetics and greatly enhanced rate capability and cycling stability for sodium ion storage. Our results afford deeper understanding of the interlayer-engineering strategy to improve the sodium ion storage performance of the VOPO nanosheets. Our results may also shed light on possible multivalent-ion based energy storage such as Mg and Al.

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“…Upon charging, the ex situ Raman spectra shows a reduction in the N−H bond signal, and it is hardly distinguished at the fully charged state E, indicating the excellent structural reversibility of our VOPO 4 ⋅2 H 2 O. Meanwhile, the peak located at around 1030 cm −1 is generated from the stretching mode of V=O in [VO 6 ] octahedron from the VOPO 4 ⋅2 H 2 O host [25] . Due to the hydrogen bond formation between the NH 4 + and VOPO 4 layer (V=O⋅⋅⋅H) and the resultant valence reduction of V from V 5+ to V 4+ , a slight red shift is thus detected for this featured peak with NH 4 + intercalation during the discharge process (B, C).…”

Section: Resultsmentioning

confidence: 97%

“…Meanwhile, the peak located at around 1030 cm À 1 is generated from the stretching mode of V=O in [VO 6 ] octahedron from the VOPO 4 •2 H 2 O host. [25] Due to the hydrogen bond formation between the NH 4 + and VOPO 4 layer (V=O•••H) and the resultant valence reduction of V from V 5 + to V 4 + , a slight red shift is thus detected for this featured peak with NH 4…”

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confidence: 99%

Reversible Ammonium Ion Intercalation/de‐intercalation with Crystal Water Promotion Effect in Layered VOPO₄⋅2 H₂O**

Pang

et al. 2023

Angew Chem Int Ed

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The non-metal NH 4 + carrier has attracted tremendous interests for aqueous energy storage owing to its light molar mass and fast diffusion in aqueous electrolytes. Previous study inferred that NH 4 + ion storage in layered VOPO 4 •2 H 2 O is impossible due to the removal of NH 4 + from NH 4 VOPO 4 leads to a phase change inevitably. Herein, we update this cognition and demonstrated highly reversible intercalation/de-intercalation behavior of NH 4 + in layered VOPO 4 •2 H 2 O host. Satisfactory specific capacity of 154.6 mAh g À 1 at 0.1 A g À 1 and very stable discharge potential plateau at 0.4 V based on reference electrode was achieved in VOPO 4 •2 H 2 O. A rocking-chair ammonium-ion full cell with the VOPO 4 •2 H 2 O//2.0 M NH 4OTf//PTCDI configuration exhibited a specific capacity of 55 mAh g À 1 , an average operating voltage of about 1.0 V and excellent long-term cycling stability over 500 cycles with a coulombic efficiency of � 99 %. Theoretical DFT calculations suggest a unique crystal water substitution process by ammonium ion during the intercalation process. Our results provide new insight into the intercalation/deintercalation of NH 4 + ions in layered hydrated phosphates through crystal water enhancement effect.

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Water/Ethanol Displacement Reactions in Vanadyl Phosphate

Cited by 19 publications

References 21 publications

A Layered Zn_0.4VOPO₄·0.8H₂O Cathode for Robust and Stable Zn Ion Storage

A Layered Zn_0.4VOPO₄·0.8H₂O Cathode for Robust and Stable Zn Ion Storage

Effective Interlayer Engineering of Two-Dimensional VOPO₄ Nanosheets via Controlled Organic Intercalation for Improving Alkali Ion Storage

Reversible Ammonium Ion Intercalation/de‐intercalation with Crystal Water Promotion Effect in Layered VOPO₄⋅2 H₂O**

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Water/Ethanol Displacement Reactions in Vanadyl Phosphate

Cited by 19 publications

References 21 publications

A Layered Zn0.4VOPO4·0.8H2O Cathode for Robust and Stable Zn Ion Storage

A Layered Zn0.4VOPO4·0.8H2O Cathode for Robust and Stable Zn Ion Storage

Effective Interlayer Engineering of Two-Dimensional VOPO4 Nanosheets via Controlled Organic Intercalation for Improving Alkali Ion Storage

Reversible Ammonium Ion Intercalation/de‐intercalation with Crystal Water Promotion Effect in Layered VOPO4⋅2 H2O**

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A Layered Zn_0.4VOPO₄·0.8H₂O Cathode for Robust and Stable Zn Ion Storage

A Layered Zn_0.4VOPO₄·0.8H₂O Cathode for Robust and Stable Zn Ion Storage

Effective Interlayer Engineering of Two-Dimensional VOPO₄ Nanosheets via Controlled Organic Intercalation for Improving Alkali Ion Storage

Reversible Ammonium Ion Intercalation/de‐intercalation with Crystal Water Promotion Effect in Layered VOPO₄⋅2 H₂O**